Scratch resistant polypropylene

ABSTRACT

Disclosed are scratch resistant polypropylene molded parts comprising a) a polypropylene substrate and incorporated therein a combination of b) an alpha, beta-unsaturated carboxylic reagent functionalized olefin polymer or copolymer, c) a primary or secondary fatty acid amide and d) a nucleating agent selected from the group consisting of sodium benzoate, 2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate, zinc glycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane and sodium salt of 1,2-dicarboxylic acid norbornane. Also disclosed is a method for providing scratch resistance to a polypropylene molded part by incorporating said additives. The polypropylene substrate is for instance polypropylene homopolymer or thermoplastic polyolefin (TPO). Component b) is for instance maleated polypropylene or the reaction product of an alpha-olefin and maleic anhydride. The fatty acid amide is for instance stearyl erucamide or oleyl palmitamide. The molded parts are suitable for automotive parts. The molded parts also advantageously contain a filler, for example talc.

This application claims priority of U.S. provisional application Nos.61/247,682, filed Oct. 1, 2009, 61/223,500, filed Jul. 7, 2009 and61/217,059, filed May 26, 2009, the contents of which applications areincorporated by reference.

The present invention is aimed at scratch resistant polypropylenecompositions. The invention is also aimed at a method of impartingscratch resistance to polypropylene compositions. The polypropylenecompositions are for example thermoplastic olefin (TPO) molded parts.The molded parts are useful for example in automotive applications.

U.S. Pat. No. 7,096,191 teaches blends of polyolefin and a reactionproduct of polyolefin and an alpha, beta unsaturated carboxylic ester,acid or anhydride, such as acrylated or maleated polypropylene.

U.S. 2006/0276571 teaches polyolefin substrates containing a carboxylicacid reagent functionalized olefin polymer and a primary or secondaryfatty acid amide.

The U.S. Patents and published applications listed herein areincorporated by reference.

SUMMARY OF THE INVENTION

Disclosed are polypropylene molded parts comprising

a) a polypropylene substrate and incorporated therein a combination of

b) an alpha, beta-unsaturated carboxylic reagent functionalized olefinpolymer or copolymer,

c) a primary or secondary fatty acid amide and

d) a nucleating agent selected from the group consisting of sodiumbenzoate, 2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate, zincglycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane andsodium salt of 1,2-dicarboxylic acid norbornane.

Also disclosed are polypropylene molded parts comprising

a) a polypropylene substrate and incorporated therein a combination of

b) an alpha, beta-unsaturated carboxylic reagent functionalized olefinpolymer or copolymer,

c) a primary or secondary fatty acid amide,

d) a nucleating agent selected from the group consisting of sodiumbenzoate, 2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate, zincglycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane andsodium salt of 1,2-dicarboxylic acid norbornane and

e) a filler.

Also disclosed is a method for providing scratch resistance to apolypropylene molded part, which method comprises incorporating intosaid polypropylene part

b) an alpha, beta-unsaturated carboxylic reagent functionalized olefinpolymer or copolymer,

c) a primary or secondary fatty acid amide and

d) a nucleating agent selected from the group consisting of sodiumbenzoate, 2,2′methylene-bis-(4,6-di-tert-butylphenyl)phosphate, zincglycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane andsodium salt of 1,2-dicarboxylic acid norbornane.

Also disclosed is a method for providing scratch resistance to apolypropylene molded part, which method comprises incorporating intosaid polypropylene part

b) an alpha, beta-unsaturated carboxylic reagent functionalized olefinpolymer or copolymer,

c) a primary or secondary fatty acid amide,

d) a nucleating agent selected from the group consisting of sodiumbenzoate, 2,2′methylene-bis-(4,6-di-tert-butylphenyl)phosphate, zincglycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane andsodium salt of 1,2-dicarboxylic acid norbornane and

e) a filler.

DETAILED DISCLOSURE

Present component a) is for instance a polypropylene homopolymer.

Polypropylene homopolymer also covers long chain branched polypropylene.

Polypropylene, can be prepared by different methods. Examples are:

Catalytic polymerization using a catalyst that normally contains one ormore than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerizationmedium. The catalysts can be used by themselves in the polymerization orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

According to a further embodiment of the present invention, component a)is a polypropylene random copolymer, alternating or segmented copolymeror block copolymer containing one or more comonomers selected from thegroup consisting of ethylene, C₄-C₂₀-α-olefin, vinylcyclohexane,vinylcyclohexene, C₄-C₂₀alkandiene, C₅-C₁₂cycloalkandiene and norbornenederivatives; the total mole amount of propylene and the comonomer(s)being 100%.

Polypropylene copolymer also covers long chain branched polypropylenecopolymer.

Examples of suitable C₄-C₂₀α-olefins are 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and4-methyl-1-pentene.

Examples of suitable C₄-C₂₀alkandienes are hexadiene and octadiene.

Examples of suitable C₅-C₁₂cycloalkandienes are cyclopentadiene,cyclohexadiene and cyclooctadiene.

Examples of suitable norbornene derivatives are5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCP) andmethylene-domethylene-hexahydronaphthaline (MEN).

A propylene/ethylene copolymer contains for example 50 to 99.9%,preferably 80 to 99.9%, in particular 90 to 99.9%, by weight ofpropylene.

A propylene copolymer wherein the comonomer is a C₉-C₂₀α-olefin such ase.g. 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene or 1-eicosene; C₉-C₂₀alkandiene,C₉-C₁₂cycloalkandiene or a norbornene derivative such as e.g.5-ethylidene-2-norbornene (ENB) ormethylene-domethylene-hexahydronaphthaline (MEN) contains preferablymore than 90 mol %, in particular 90 to 99.9 mol % or 90 to 99 mol %, ofpropylene.

A propylene copolymer wherein the comonomer is a C₄-C₈α-olefin such ase.g. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or4-methyl-1-pentene; vinylcyclohexane, vinylcyclohexene, C₄-C₈alkandieneor C₅-C₈cycloalkandiene contains preferably more than 80 mol %, inparticular 80 to 99.9 mol % or 80 to 99 mol %, of propylene.

Further examples of component a) are propylene/isobutylene copolymer,propylene/butadiene copolymer, propylene/cycloolefin copolymer,terpolymers of propylene with ethylene and a diene such as hexadiene,dicyclopentadiene or ethylidene-norbornene; propylene/1-olefincopolymers where the 1-olefin is generated in situ; and propylene/carbonmonoxide copolymers.

The polypropylenes of the present invention are in particularpolypropylene homopolymers, polypropylene impact (heterophasic)copolymers, blends thereof and TPO's such as blends of polypropylenehomopolymers and impact modifiers such as EPDM or ethylene/alpha-olefincopolymers.

TPO (thermoplastic olefin) is for example about 10 to about 90 partspropylene homopolymer, copolymer or terpolymer, and about 90 to about 10parts (by weight) of an elastomeric copolymer of ethylene and a C₃-C₈alpha-olefin. The elastomeric copolymer is for instanceethylene/propylene copolymer (EPM) or ethylene/propylene/non-conjugateddiene (EPDM). TPO is disclosed for example in U.S. Pat. No. 6,048,942,incorporated by reference.

Component b) is an alpha, beta-unsaturated carboxylic reagentfunctionalized olefin polymer or copolymer.

The carboxylic reagent functionalized olefin polymers or copolymers aredisclosed for instance in U.S. Pat. No. 7,026,391, incorporated hereinby reference.

The olefin polymers or copolymers of the functionalized olefin polymersor copolymers are for example the polypropylenes of component a).

The functionalized olefin polymers or copolymers are for example thereaction product of at least one polypropylene and at least one alpha,beta-unsaturated carboxylic reagent, such as a carboxylic acid, ester oranhydride.

In one embodiment, the number average molecular weight of thepolypropylenes utilized in this component may range from about 2,000 toabout 10,000. These polymers typically have a melt flow from about 8 toabout 40, or from about 10 to about 35, or from about 15 to about 30g/10 min. The amount of carboxylic reagent reacted with thepolypropylene may range from about 0.5% to about 30% or from about 1% toabout 20%, or from about 2% to about 15%, or from about 4% to about 10%by weight.

The alpha, beta unsaturated carboxylic reagent may be a mono- ordicarboxylic reagent. The carboxylic reagents include carboxylic acids,esters and salts. The monobasic alpha, beta-unsaturated carboxylicreagents include acrylic, methacrylic, annamic, crotonic acids andesters, such as esters having from 1 to about 12 carbon atoms, and saltssuch as sodium, calcium or magnesium salts. Examples of dicarboxylicreagents include maleic acid, maleic anhydride, fumaric acid, mesaconicacid, himic anhydride, itaconic acid, citraconic acid, itaconicanhydride, citraconic anhydride, monomethyl maleate, monosodium maleate,etc. Particularly preferred alpha, beta-unsaturated carboxylic reagentsare acrylic acid, methacrylic acid, acrylic esters, methacrylic estersand maleic anhydride.

The reaction between the carboxylic reagent and the polypropylenepolymer or copolymer can be effected by means known to those skilled inthe art. For example, the reaction can be conducted in solution by amelt process in the presence of a free radical initiator. The freeradical initiators usually are either peroxides or various organic azocompounds. The amount of initiator utilized is generally from about0.01% to about 5% by weight based on the combined weight of thepolyolefin and the carboxylic reagent.

The reaction between the carboxylic reagent and the polypropylenepolymer or copolymer is referred to as “grafting”. For example, thepresent functionalized polypropylene polymers or copolymers arepolypropylene polymers or copolymers grafted with acrylic acid,methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxypropylmethacrylate, butyl acrylate or maleic anhydride. In the case of forexample grafting with maleic anhydride, this is termed “maleated”.

Examples of acrylated polyolefins are the POLYBOND polymers availablefrom Uniroyal Chemical Company. A particularly useful polymer isPOLYBOND 1002, which has a melt flow of 15-25 g/10 min and an acrylicacid content 5.5% to 7.0% by weight. An example of a commerciallyavailable maleic acid grafted polypropylene is Epolene E-43 wax fromEastman Chemical Products, Inc. EPOLENE E-43 has an acid number of 47and an approximate number average molecular weight of 4500. EPOLENE C-16and C-18 waxes are maleic acid grafted polyethylenes with approximatemolecular weights of 8000 and 4000, respectively. Maleatedethylene-propylene elastomers also are useful, and such elastomers areavailable from Exxon Chemical Company under identification numbers99-10, 99-14 and 99-26. These copolymers contain 77%, 64% and 43% ofethylene, respectively, and the maleated products contain 0.76%, 0.56%and 0.35% of maleic acid or anhydride, respectively.

Other examples of commercially available maleic acid anhydride graftedpolyolefins include KRATON FG1901X from Shell which is often referred toas a maleated selectively hydrogenated SEBS copolymer; terpolymersavailable from CdF Chimie under designations such as LOTADER 3200(prepared from a mixture of 88% by weight ethylene, 9% by weight butylacrylate and 3% maleic anhydride), LOTADER 6600 (70% ethylene, 27%acrylic ester and 3% maleic anhydride) etc.; ethylene vinyl acetatecopolymers grafted with maleic anhydride (EVA-MAH) are available fromQuantum Chemical Corp.

Alternatively, the functionalized olefin polymers or copolymers ofcomponent b) are the reaction products of an alpha-olefin with an alpha,beta-unsaturated carboxylic reagent as described above. The reaction iseffected by means known in the art. For example, the reaction can beconducted by a melt process in the presence of a free radical initiator.The radical initiators are for example peroxides or organic azocompounds. Again, the unsaturated carboxylic reagents are for exampleacrylic acid, methacrylic acid, acrylic esters, methacrylic esters ormaleic anhydride.

For instance, the alpha-olefin is from C₃ up to about C₃₃, for examplethe alpha-olefin is a C₁₈-C₂₆ alpha-olefin, for example a C₂₂₋₂₆ or aC₁₈ alpha-olefin.

For instance, the functionalized olefin is a maleated alpha-olefin, thatis, the reaction product of an alpha-olefin and maleic anhydride. Forexample the maleated alpha-olefin is of the formula

where

R is C₁₆ to C₂₄ alkyl and

n is an integer such that the average molecular weight is from about20,000 to about 50,000.

The primary or secondary fatty acid amides are for example where thefatty group of the fatty acids are C₁₁ to C₂₁ alkyl or alkenyl.

The primary or secondary fatty acid amide is for example at least onecompound selected from the group consisting of oleamide, erucamide,stearamide, behenamide, oleyl palmitamide, stearyl erucamide,ethylene-bis-stearamide and ethylene-bis-oleamide.

In particular, the present fatty acid amides are secondary fatty acidamides, for example stearyl erucamide or oleyl palmitamide.

Suitable fatty acid amides are for example disclosed in U.S. Pat. No.6,228,915, the relevant disclosures of which are hereby incorporated byreference.

Alkyl is straight or branched chain and is for example methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl ordocosyl.

Alkenyl is ethylenically unsaturated alkyl, for example allyl.

The weight:weight ratio of the functionalized olefin polymer orcopolymer additive to the primary or secondary fatty acid amide additiveis for example from about 20:1 to about 1:20, from about 10:1 to about1:10, from about 1:1 to about 20:1, for example from about 1:1 to about15:1, from about 1:1 to about 10:1, from about 1:1 to about 7:1, or fromabout 1:1 to about 5:1. For instance, the weight:weight ratio of thefunctionalized olefin to the primary or secondary fatty acid amide isabout 1.5:1, about 2:1, about 3:1, or about 4:1.

The total of the functionalized olefin polymer or copolymer b) andprimary or secondary fatty acid amide additive c) combination to beincorporated into the polypropylene substrate is for example from about1% to about 15% by weight, based on the weight of the polypropylenesubstrate. For example, the additive combination is present from about1% to about 10%, from about 3% to about 7%, or from about 3% to about 5%by weight, based on the weight of the polypropylene substrate. Forinstance, the present combination of b) and c) is present from about 1%to about 3%, from about 1% to about 5%, or from about 1% to about 7% byweight, based on the weight of the polypropylene substrate.

Component d), the present nucleating agents, are selected from sodiumbenzoate, 2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate and zincglycerolate.

It is contemplated that other known nucleating agents would also performwell in the present formulations. Such further nucleating agents aredisclosed for example in U.S. Pat. Nos. 6,465,551 and 6,878,443,incorporated herein by reference. Further possible nucleating agents arefor instance dibenzylidene sorbitol compounds, for example amonomethyldibenzylidene sorbitol such as1,3:2,4-bis(p-methylbenzylidene) sorbitol or a dimethylbenzylidenesorbitol such as 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol. Otherknown nucleating agents are [2.2.1]heptane-bicyclodicarboxylic acid(1,2-dicarboxylic acid norbornane) and 1,2-dicarboxylic acidcyclohexane. Other metal salts of organic acids in addition to sodiumbenzoate may also be suitable, for instance metal salts of1,2-dicarboxylic acid cyclohexane and 1,2-dicarboxylic acid norbornane,for instance sodium or calcium salts. Other cyclic bis-phenol phosphatesmay also be suitable.

The present nucleating agents are employed for instance at a level offrom about 1 ppm to about 50,000 ppm by weight, based on the weight ofthe polypropylene. For instance, the present nucleating agents areemployed at a level of from about 10 ppm to about 20,000 ppm, from about100 ppm to about 10,000 ppm or from about 1000 ppm to about 5000 ppm byweight, based on the weight of the polypropylene.

The additives of the invention may be added to the polypropylenesubstrate individually or mixed with one another. If desired, theindividual components can be mixed with one another before incorporationinto the polypropylene for example by dry blending, compaction or in themelt.

The incorporation of the additives of the invention is carried out byknown methods such as dry blending in the form of a powder, or wetmixing in the form of solutions, dispersions or suspensions for examplein an inert solvent, water or oil. The additives of the invention may beincorporated, for example, before or after molding or also by applyingthe dissolved or dispersed additive or additive mixture to thepolypropylene material, with or without subsequent evaporation of thesolvent or the suspension/dispersion agent. They may be added directlyinto the processing apparatus (e.g. extruders, internal mixers, etc.),e.g. as a dry mixture or powder or as a solution or dispersion orsuspension or melt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is preferably carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the additives to the polypropylene substrate can becarried out in all customary mixing machines in which the polypropyleneis melted and mixed with the additives. Suitable machines are known tothose skilled in the art. They are predominantly mixers, kneaders andextruders.

Processing includes extrusion, co-kneading, pultrusion, compressionmolding, sheet extrusion, thermoforming, injection molding or rotationalmolding. The process is preferably carried out in an extruder byintroducing the additives during melt processing.

Particularly preferred processing machines are single-screw extruders,contrarotating and corotating twin-screw extruders, rotomolding devices,planetary-gear extruders, ring extruders or cokneaders. It is alsopossible to use processing machines provided with at least one gasremoval compartment to which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length 1-60 screw diameters, preferably 35-48screw diameters. The rotational speed of the screw is preferably 10-600rotations per minute (rpm), very particularly preferably 25-300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components are added, these can be premixed or addedindividually.

The additives of the invention can also be sprayed onto thepolypropylene substrate. They are able to dilute other additives (forexample optional conventional additives) or their melts so that they canbe sprayed also together with these additives onto the substrate.Addition by spraying during the deactivation of the polymerizationcatalysts is particularly advantageous; in this case, the steam evolvedmay be used for deactivation of the catalyst. In the case of sphericallypolymerized polypropylenes it may, for example, be advantageous to applythe additives of the invention, optionally together with otheradditives, by spraying.

The additives of the invention and optional further additives can alsobe added to the polypropylene in the form of a masterbatch(“concentrate”) which contains the components in a concentration of, forexample, about 1% to about 40% and preferably about 2% to about 20% byweight incorporated in a polymer. The polymer must not necessarily beidentical to the polypropylene where the additives are added finally. Insuch operations, the polymer can be used in the form of powder,granules, solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polypropylene,with or without subsequent evaporation of the solvent. A furtherpossibility for incorporating the additives of the invention intopolypropylene substrates is to add them before, during or directly afterthe polymerization of the corresponding monomers or prior tocrosslinking. In this context the additives of the invention can beadded as is or else in encapsulated form (for example in waxes, oils orpolymers).

The polypropylenes containing the additives of the invention describedherein can be used for the production of moldings, rotomolded articles,injection molded articles, blow molded articles, profiles, and the like.

The polypropylenes of the present invention may optionally also containfrom about 0.01 to about 5%, preferably from about 0.025 to about 2%,and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(αα-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl) butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. Benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzy)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxy-lauric acid anilide,4-hydroxy-stearic acid anilide,2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine andoctyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.13. Esters of β(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexane-dial, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hy-droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known commercialhydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in, U.S.Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615;3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589;4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471;5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349;5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987, 5,977,219 and6,166,218 such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-αcumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates and malonates, for example, α-cyano-β,β-diphenylacrylicacid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvor® PR25,dimethyl p-methoxybenzylidenemalonate (CAS# 7443-25-6), and Sanduvor®PR31, di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate (CAS #147783-69-5).

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amine stabilizers, for example4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylyamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-amino-propylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

The sterically hindered amine may also be one of the compounds describedin U.S. Pat. No. 5,980,783, the relevant parts of which are herebyincorporated by reference, that is compounds of component I-a), I-b),I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), inparticular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2,1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed oncolumns 64-72 of said U.S. Pat. No. 5,980,783.

The sterically hindered amine may also be one of the compounds describedin U.S. Pat. Nos. 6,046,304 and 6,297,299, the disclosures of which arehereby incorporated by reference, for example compounds as described inclaim 10 or 38 or in Examples 1-12 or D-1 to D-5 therein.

2.7. Sterically hindered amines substituted on the N-atom by ahydroxy-substituted alkoxy group, for example compounds such as1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidinewith a carbon radical from t-amylalcohol,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate and2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine.

2.8. Oxamides, for example 4, 4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known commercialtris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in,U.S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891;5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503;5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,736,597;5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,242,598 and6,255,483, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,Cyasorb® 1164, Cytec Corp,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyl-oxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxy-propyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenynl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(*denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis-{2,4-bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazineand 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide,N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba SpecialtyChemicals Corp.), tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamineand the N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-α-phenylnitrone,N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone,N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridcylnitrone,N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone,N-hexadecyl-α-heptadecylnitrone, N-ocatadecyl-α-pentadecylnitrone,N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone,N-methyl-α-heptadecylnitrone and the nitrone derived fromN,N-dialkylhydro-xylamine derived from hydrogenated tallow amine.

7. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

8. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643 5,369,1595,356,966 5,367,008 5,428,177 or 5,428,162 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, Irganox®HP-136, Ciba Specialty Chemicals Corp., and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

9. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

10. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

11. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

12. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example, calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

13. Other nucleating agents, for example inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate; polymeric compounds such as ioniccopolymers (ionomers).

14. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

The present formulations advantageously comprise a filler, for examplecoated or uncoated talc.

The fillers may also be for example natural or synthetic phyllosilicatesor a mixture of such phyllosilicates. Fillers of special interest arefor example layered silicate clays. Of very special interest aremontmorillonite, bentonite, beidelite, mica, hectorite, saponite,nontronite, sauconite, vermiculite, ledikite, magadite, kenyaite,stevensite, volkonskoite, hydrotalcite, illite, kaolinite, wollastonite,attapulgite, talc or silica or a mixture thereof.

The filler is present from about 1% to about 50% by weight, based on theweight of the polypropylene. For instance, the filler is present atabout 5%, about 10%, about 15%, about 20% or about 25% and within all ofthese possible ranges, based on the weight of the polypropylene.

15. Dispersing Agents, such as polyethylene oxide waxes or mineral oil.

16. Other additives, for example plasticizers, lubricants, emulsifiers,pigments, dyes, optical brighteners, rheology additives, catalysts,flow-control agents, slip agents, crosslinking agents, crosslinkingboosters, halogen scavengers, smoke inhibitors, flameproofing agents,antistatic agents, clarifiers such as substituted and unsubstitutedbisbenzylidene sorbitols, benzoxazinone UV absorbers such as2,2′-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS#18600-59-4), and blowing agents.

The present polypropylene compositions exhibit good weatherability(stability towards heat, oxygen and light), scratch resistance, goodprocessability, good mechanical strength, good gloss retention, and arenon-sticky. The polypropylene molded parts are suitable for example forautomotive applications, i.e. bumper fascia and the like.

EXAMPLES

The following Examples illustrate the present invention. The Examplesare not meant to limit the scope of the present invention. Unlessotherwise indicated, all percentages are in parts by weight.

Example 1 Thermoplastic Olefin (TPO)

Test formulations are prepared in unfilled TPO via melt compounding. TheTPO is polypropylene containing about 8-10% by weight elastomer with 2%by weight carbon black. The TPO and the additives are mixed at 204° C.to 230° C. in an 18 mm twin screw extruder. The pellets are driedovernight at 80° C. The TPO formulations are injection molded at atemperature of 450° F., injection and holding pressures at 1000 psi,back pressure of 50 psi, screw speed 150 rpm, clamping unit setting at287.5 mm, shot size 70 and chiller temperature of 45° F. to provide 4inch by 6 inch smooth, flat plaques.

The plaques are tested according to the five finger scratch test.

Standard Five Finger Scratch test guidelines (Daimler ChryslerCorporation Test Number LP-463DD-18-1, dated 2002-07-24).

Rating Scratch Width Whitening 1 (best) <0.2 mm wide, almost invisiblenone 2 0.2-0.3 mm wide, slight deformation, none visible at close range3 0.3-0.4 mm wide, clearly visible 4 0.4-0.5 mm wide visible whiteningover entire scratch 5 (worst) >0.5 mm wide white over entire scratch andpossibly accompanied by debris

The scratch test is performed at 10 Newtons at 0 min. (right off themold), 5 min., 10 min., 20 min. and overnight (24 hours). The samplesare stored at ambient conditions.

The following formulations (weight percent) are prepared:

Formulation TPO anti-scratch additive NU1 NU2 NU3 1 100 — — — — 2 97 3 —— — 3 96.85 3 0.15 — — 4 96.7 3 0.3  — — 5 96.85 3 — 0.15 — 6 96.7 3 —0.3  — 7 96.85 3 — — 0.15 8 96.7 3 — — 0.3 

The results for scratch resistance at 10 Newtons is as follows:

Formulation rating at time 0 rating at 24 hours 1 5 5 2 4 2 3 1-2 1-2 41-2 1-2 5 1-2 1-2 6 1-2 1-2 7 1-2 1-2 8 1-2 1-2

Formulation 1 shows no scratch resistance at 10 N.

Formulation 2, with no nucleating agent showed poor scratch performanceat time 0. A certain level of scratch resistance is achieved uponstoring 24 hours.

In Formulations 3-8, containing both anti-scratch additive andnucleating agent, good scratch resistance is achieved at time 0, rightoff the mold. This scratch resistance is better than that of Formulation2 after 24 hours. The same good scratch performance is observed afterstoring 24 hours. That is, scratch resistance is achieved with thecompositions of the present invention without conditioning, withoutstoring or curing at room temperature or elevated temperatures.

The anti-scratch additive is a 2:1 weight blend of maleatedpolypropylene to stearyl erucamide.

NU1 is sodium benzoate. NU2 is2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate. NU3 is zincglycerolate.

Example 2 Filled Thermoplastic Olefin (TPO)

Test formulations are prepared in TPO via melt compounding. The TPO ispolypropylene containing about 8-10% by weight elastomer with 2% byweight carbon black. The TPO and the additives are mixed at 204° C. to230° C. in an 18 mm twin screw extruder. Also added is 30% by weightuncoated talc filler, based on the weight of the TPO. The pellets aredried overnight at 80° C. The TPO formulations are injection molded at atemperature of 450° F., injection and holding pressures at 1000 psi,back pressure of 50 psi, screw speed 150 rpm, clamping unit setting at287.5 mm, shot size 70 and chiller temperature of 45° F. to provide 4inch by 6 inch smooth, flat plaques.

The plaques are tested according to the five finger scratch test afterstoring for 24 hours.

Formulation TPO anti-scratch additive NU1 NU2 9 100 — — — 10 98.5 1.5 —— 11 97.0 3.0 — — 12 98.35 1.5 — 0.15 13 98.35 1.5 0.15 — 14 99.85 — —0.15 15 99.85 — 0.15 —

The results for scratch resistance at 20, 15 and 10 Newtons are asfollows:

Formulation 20 N 15 N 10 N 9 5 5 4 10 5 4 2-3 11 5 2-3 1-2 12 4-5 1 1 134-5 1 1 14 5 5 3-4 15 5 5 3-4

The anti-scratch additive is as in Example 1.

Formulations 12 and 13 are of the present invention and showsubstantially reduced whitening according to the 5 finger scratch test.

Formulations 12 and 13 exhibit synergistic results compared toformulations 10, 14 and 15.

1. A thermoplastic olefin molded part comprising a) a thermoplasticolefin substrate and incorporated therein a combination of b) maleatedpolypropylene, c) stearyl erucamide and d) a nucleating agent selectedfrom the group consisting of sodium benzoate,2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate and zincglycerolate, where the nucleating agent is present from 0.15 to 0.3weight percent and components b) and c) together are present from 1.5 to3.0 weight percent, the weight percents being based on the total weightof components a), b), c) and d).
 2. A molded part according to claim 1where the weight:weight ratio of the maleated polypropylene to thestearyl erucamide is from about 1:1 to about 20:1.
 3. A molded partaccording to claim 2 where the weight:weight ratio is from about 1:1 toabout 5:1.
 4. A molded part according to claim 1 where the nucleatingagent is sodium benzoate.
 5. A molded part according to claim 1 wherethe nucleating agent is2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate.
 6. A method forproviding scratch resistance to a thermoplastic olefin molded part,which method comprises incorporating into a) a thermoplastic olefinsubstrate b) maleated polypropylene, c) stearyl erucamide and d) anucleating agent selected from the group consisting of sodium benzoate,2,2′methylene-bis-(4,6-di-tert-butylphenyl)phosphate and zincglycerolate, where the nucleating agent is present from 0.15 to 0.3weight percent and components b) and c) together are present from 1.5 to3.0 weight percent, the weight percents being based on the total weightof components a), b), c) and d).
 7. A molded part according to claim 1further comprising e) a filler.
 8. A method according to claim 6 furthercomprising the incorporation of e) a filler.
 9. A molded part accordingto claim 1 where the nucleating agent is zinc glycerolate.